Recording sheets containing phosphonium compounds

Abstract: Disclosed is a recording sheet which comprises a base sheet, a phosphonium compound, an optional pigment, and an optional binder. In a preferred embodiment, the phosphonium compound is selected from the group consisting of wherein R is an alkyl group, X is an anion, and all four R groups are the same; wherein R is an alkyl group, wherein all three R groups are the same, wherein R is not the same as R', X is an anion, and R' is selected from the group consisting of alkyl groups, substituted alkyl groups, arylalkyl groups, and substituted arylalkyl groups; wherein Ar is an aryl group or a substituted aryl group, X is an anion, and all four Ar groups are the same; wherein Ar is an aryl group or a substituted aryl group, wherein all three Ar groups are the same, X is an anion, and R' is selected from the group consisting of alkyl groups, substituted alkyl groups, arylalkyl groups, and substituted arylalkyl groups; and mixtures thereof.

Description: The present invention is directed to recording sheets, such as transparency materials, filled plastics, papers, and the like. More specifically, the present invention is directed to recording sheets particularly suitable for use in ink jet printing processes. Recording sheets suitable for use in ink jet printing are known. For example, US-A-4,740,420 (Akutsu et al.) discloses a recording medium for ink jet printing comprising a support material containing at least in the surface portion thereof a water soluble metal salt with the ion valence of the metal thereof being 2 to 4 and a cationic organic material. The cationic organic materials include salts of alkylamines, quaternary ammonium salts, polyamines, and basic latexes. US-A-4,576,867 (Miyamoto) discloses an ink jet recording paper with improved water resistance and sunlight fastness of the image formed on the paper wherein the recording paper has attached to its surface a cationic resin of the formula wherein R 1 , R 2 , and R 3 represent alkyl groups, m represents a number of 1 to 7, and n represents a number of 2 to 20, and Y represents an acid residue. EP-A-506,034 discloses a method for forming images by thermal transfer process. The method comprises the steps of of providing a printing sheet having an image-receiving layer on one side thereof, providing an ink ribbon having a dye layer comprising a hydrophilic cationic dye, contacting the ink ribbon with the image receiving layer, and applying thermal energy to the ink ribbon in an imagewise pattern to thermally transfer the dye from the ink ribbon to the image-receiving layer. The image-receiving layer comprises at least a layer compound which has ion exchangeability with the cationic dye, so that the dye image is fixed through the ion exchange. While known compositions and processes are suitable for their intended purposes, a need remains for improved recording sheets. In addition, there is a need for improved recording sheets suitable for use in ink jet printing processes. Further, a need remains for recording sheets for ink jet printing with a high degree of waterfastness. Additionally, there is a need for paper recording sheets for ink jet printing with reduced showthrough of the images on the side of the paper opposite to that printed. There is also a need for recording sheets for ink jet printing with enhanced optical density. It is an object of the present invention to provide recording sheets with the above noted advantages. The present invention provides a printing process which comprises applying a recording liquid to a recording sheet comprising a base sheet and a phosphonium compound, in an imagewise pattern, characterised by comprising (1) incorporating the recording sheet into an ink jet printing apparatus containing an aqueous ink, and (2) causing droplets of the ink to be ejected in an imagewise pattern onto the recording sheet, thereby generating images on the recording sheet. In a preferred embodiment, the phosphonium compound is selected from the group consisting of wherein R is an alkyl group, X is an anion, and all four R groups are the same; wherein R is an alkyl group, wherein all three R groups are the same, wherein R is not the same as R', X is an anion, and R' is selected from the group consisting of alkyl groups, substituted alkyl groups, arylalkyl groups, and substituted arylalkyl groups; wherein Ar is an aryl group or a substituted aryl group, X is an anion, and all four Ar groups are the same; wherein Ar is an aryl group or a substituted aryl group, wherein all three Ar groups are the same, X is an anion, and R' is selected from the group consisting of alkyl groups, substituted alkyl groups, arylalkyl groups, and substituted arylalkyl groups; and mixtures thereof. The recording sheets of the present invention comprise a substrate and at least two coating layers on one or both surfaces of the substrate. Any suitable substrate can be employed. Examples include transparent materials, such as polyester, including Mylar™, available from E.I. Du Pont de Nemours & Company, Melinex™, available from Imperial Chemicals, Inc., Celanar™, available from Celanese Corporation, polycarbonates such as Lexan™, available from General Electric Company, polysulfones, such as those available from Union Carbide Corporation, polyether sulfones, such as those prepared from 4,4'-diphenyl ether, such as Udel™, available from Union Carbide Corporation, those prepared from disulfonyl chloride, such as Victrex™, available from ICI America Incorporated, those prepared from biphenylene, such as Astrel™, available from 3M Company, poly (arylene sulfones), such as those prepared from crosslinked poly(arylene ether ketone sulfones), cellulose triacetate, polyvinylchloride cellophane, polyvinyl fluoride, polyimides, and the like, with polyester such as Mylar™ being preferred in view of its availability and relatively low cost. The substrate can also be opaque, including opaque plastics, such as Teslin™, available from PPG Industries, and filled polymers, such as Melinex®, available from ICI. Filled plastics can also be employed as the substrate, particularly when it is desired to make a "never-tear paper" recording sheet. Paper is also suitable, including plain papers such as Xerox® 4024, diazo papers, or the like. In one embodiment of the present invention, the substrate comprises sized blends of hardwood kraft and softwood kraft fibers containing from about 10 to 90 percent by weight soft wood and from about 10 to about 90 percent by weight hardwood. Examples of hardwood include Seagull® W dry bleached hardwood kraft, present in one embodiment in an amount of about 70 percent by weight. Examples of softwood include La Tuque® dry bleached softwood kraft, present in one embodiment in an amount of about 30 percent by weight. These substrates can also contain fillers and pigments in any effective amounts, typically from about 1 to about 60 percent by weight, such as clay (available from Georgia Kaolin Company, Astro-fil® 90 clay, Engelhard Ansilex® clay), titanium dioxide (available from Tioxide Company-Anatase® grade AHR), calcium silicate CH-427-97-8, XP-974 (J.M. Huber Corporation), and the like. The sized substrates can also contain sizing chemicals in any effective amount, typically from about 0.25 percent to about 25 percent by weight of pulp, such as acidic sizing, including Mon® size (available from Monsanto Company), alkaline sizing such as Hercon-7®6 (available from Hercules Company), Alum® (available from Allied Chemicals as Iron free alum), retention aid (available from Allied Colloids as Percol® 292), and the like. The preferred internal sizing degree of papers selected for the present invention, including commercially available papers, varies from about 0.4 to about 5,000 seconds, and papers in the sizing range of from about 0.4 to about 300 seconds are more preferred, primarily to decrease costs. Preferably, the selected substrate is porous, and the porosity value of the selected substrate preferably varies from about 100 to about 1,260 ml/min and preferably from about 50 to about 600 ml/min to enhance the effectiveness of the recording sheet in ink jet processes. Preferred basis weights for the substrate are from about 40 to about 400 g/m 2 , although the basis weight can be outside of this range. Illustrative examples of commercially available internally and externally (surface) sized substrates suitable for the present invention include Diazo papers, offset papers, such as Great Lakes® offset, recycled papers, such as Conservatree®, office papers, such as Automimeo®, Eddy® liquid toner paper and copy papers available from companies such as Nekoosa, Champion, Wiggins Teape, Kymmene, Modo, Domtar, Veitsiluoto and Sanyo, and the like, with Xerox® 4024™ papers and sized calcium silicate-clay filled papers being particularly preferred in view of their availability, reliability, and low print through. Pigmented filled plastics, such as Teslin® (available from PPG industries), are also preferred as supporting substrates. The substrate can be of any effective thickness. Typical thicknesses for the substrate are from about 50 to about 500 µm, and preferably from about 100 to about 125 µm, although the thickness can be outside these ranges. Situated on the substrate of the present invention is one or more phosphonium compounds. Monophosphonium compounds containing one cationic phosphonium moiety are suitable, as are diphosphonium compounds containing two cationic phosphonium moieties and polyphosphonium compounds containing more than two cationic phosphonium moieties. Examples of suitable phosphonium compounds include those of the formula wherein R is an alkyl group, preferably with from 1 to about 35 carbon atoms, more preferably with from 1 to about 25 carbon atoms, X is an anion, and all four R groups are the same. Examples of suitable anions include halide anions, such as fluoride, chloride, bromide, iodide, and astatide, sulfate, alkosulfate, such as methylsulfate and ethylsulfate, sulfite, phosphate, phosphite, perhalate, such as perchlorate, perbromate, periodate, and the like, halate, such as chlorate and the like, halite, such as bromite and the like, fluoroborate, and the like. Specific examples of materials of Formula I include tetramethyl phosphonium bromide (Aldrich Chemical Co. 28,826-8), tetramethyl phosphonium chloride (Aldrich 28,827-6), tetraethyl phosphonium bromide (Aldrich 33,365-4), tetraethyl phosphonium chloride (Aldrich 32,539-2), tetraethyl phosphonium iodide (Aldrich 32,540-6), tetrabutyl phosphonium bromide (Aldrich 18,913-8), tetrabutyl phosphonium chloride (Aldrich 14,480-0), and the like. Also suitable are phosphonium compounds of the formula wherein R is an alkyl group, preferably with from 1 to about 25 carbon atoms, more preferably from 1 to about 18 carbon atoms, and wherein all three R groups are the same, X is an anion, R' is selected from the group consisting of alkyl groups, preferably with from 1 to about 25 carbon atoms, more preferably from 1 to about 18 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, hexyl, and the like, and including cyclic alkyl groups, such as cyclopropyl, cyclohexyl, and the like, and including unsaturated alkyl groups, such as vinyl (H 2 C=CH-), allyl (H 2 C=CH-CH 2 -), propynyl (HC≡-C-CH 2 -), and the like, arylalkyl groups, preferably with from 7 to about 25 carbon atoms, more preferably with from 7 to about 19 carbon atoms, such as benzyl and the like, substituted alkyl groups, preferably with from 1 to about 25 carbon atoms, more preferably from 1 to about 18 carbon atoms, substituted arylalkyl groups, preferably with from 7 to about 25 carbon atoms, more preferably with from 7 to about 19 carbon atoms, with examples of substituents including silyl groups, halide atoms, such as fluoride, chloride, bromide, iodide, and astatide, nitro groups, amine groups, including primary, secondary, and tertiary amines, hydroxy groups, alkoxy or ether groups, aldehyde groups, ketone groups, ester groups, amide groups, carboxylic acid groups, and the like, with specific examples of substituted alkyl and arylalkyl groups including bromomethyl, chloromethyl, 3-bromopropyl, 3-bromobutyl, 4-bromobutyl, 2-hydroxyethyl, 2-(dimethylamino)ethyl, of the formula 3-(dimethylamino)propyl, 3-hydroxy-2-methylpropyl, of the formula formyl methyl, of the formula methoxy methyl (CH 3 -O-CH 2 -), acetonyl, of the formula carbomethoxymethyl, of the formula ethoxy carbonyl methyl (also called carbethoxy methyl), of the formula tert-butoxy carbonyl methyl, of the formula phenacyl, of the formula dioxane derivatives of alkyls such as 2-(1,3-dioxan-2-yl)ethyl, of the formula and 1,3-dioxolan-2-yl methyl, of the formula vinyl (H 2 C=CH-), allyl (H 2 C=CH-CH 2 -), propynyl derivatives such as propargyl (HC≡C-CH 2 -), 3-trimethyl silyl-2-propynyl, of the formula xylylene derivatives, such as p-xylylene bis (triphenyl phosphonium bromide, of the formula 2-hydroxybenzyl, of the formula 4-ethoxybenzyl, of the formula 4-butoxybenzyl, and the like. Examples of suitable anions include halide anions, such as fluoride, chloride, bromide, iodide, and astatide, sulfate, alkosulfate, such as methylsulfate and ethylsulfate, sulfite, phosphate, phosphite, perhalate, such as perchlorate, perbromate, periodate, and the like, halate, such as chlorate and the like, halite, such as bromite and the like, fluoroborate, and the like. Specific examples of materials of Formula II include hexadecyl tributyl phosphonium bromide (Aldrich 27,620-0), stearyl tributyl phosphonium bromide (Aldrich 29,303-2), and the like. Also suitable are phosphonium compounds of the formula wherein Ar is an aryl group, preferably with from 6 to about 35 carbon atoms, more preferably with from 6 to about 25 carbon atoms, even more preferably with from 6 to about 18 carbon atoms, or a substituted aryl group, preferably with from 6 to about 35 carbon atoms, more preferably with from 6 to about 25 carbon atoms, even more preferably with from 6 to about 18 carbon atoms, X is an anion, and all four Ar groups are the same. Examples of suitable anions include halide anions, such as fluoride, chloride, bromide, iodide, and astatide, sulfate, alkosulfate, such as methylsulfate and ethylsulfate, sulfite, phosphate, phosphite, perhalate, such as perchlorate, perbromate, periodate, and the like, halate, such as chlorate and the like, halite, such as bromite and the like, fluoroborate, and the like. Examples of suitable substituents include alkyl groups, silyl groups, halide atoms, such as fluoride, chloride, bromide, iodide, and astatide, nitro groups, amine groups, including primary, secondary, and tertiary amines, hydroxy groups, alkoxy or ether groups, aldehyde groups, ketone groups, ester groups, amide groups, carboxylic acid groups, and the like. Specific examples of materials of Formula III include tetraphenyl phosphonium bromide (Aldrich 21,878-2), tetraphenyl phosphonium chloride (Aldrich 21879-0), tetraphenyl phosphonium Iodide (Aldrich 21880-4), and the like. Also suitable are phosphonium compounds of the formula wherein Ar is an aryl group, preferably with from 6 to about 35 carbon atoms, more preferably with from 6 to about 25 carbon atoms, even more preferably with from 6 to about 18 carbon atoms, or a substituted aryl group, preferably with from 6 to about 35 carbon atoms, more preferably with from 6 to about 25 carbon atoms, even more preferably with from 6 to about 18 carbon atoms, X is an anion, R' is as defined herein with respect to Formula II, and all three Ar groups are the same. Examples of suitable anions include halide anions, such as fluoride, chloride, bromide, iodide, and astatide, sulfate, alkosulfate, such as methylsulfate and ethylsulfate, sulfite, phosphate, phosphite, perhalate, such as perchlorate, perbromate, periodate, and the like, halate, such as chlorate and the like, halite, such as bromite and the like, fluoroborate, and the like. Specific examples of materials of Formula IV include methyl triphenyl phosphonium bromide (Aldrich 13,007-9), methyl triphenyl phosphonium iodide (Aldrich 24,505-4), ethyl triphenyl phosphonium bromide (Aldrich E5,060-4), n-propyl triphenyl phosphonium bromide (Aldrich 13,156-3), isopropyl triphenyl phosphonium iodide (Aldrich 37,748-1), cyclopropyl triphenyl phosphonium bromide (Aldrich 15,731-7), n-butyl triphenyl phosphonium bromide (Aldrich B10, 280-6), isobutyl triphenyl phosphonium bromide (Aldrich 37,750-3), hexyl triphenyl phosphonium bromide (Aldrich 30,144-2), benzyl triphenyl phosphonium chloride (Aldrich B3, 280-7), bromomethyl triphenyl phosphonium bromide (Aldrich 26, 915-8), chloromethyl triphenyl phosphonium chloride (Aldrich C5,762-6), 3-bromopropyl triphenyl phosphonium bromide (Aldrich 13,525-9), 3-bromobutyl triphenyl phosphonium bromide (Aldrich 30, 537-5), 4-bromobutyl triphenyl phosphonium bromide (Aldrich 27, 213-2), 2-dimethyl aminoethyl triphenyl phosphonium bromide (Aldrich 21,544-9), [(3-dimethyl amino) propyl] triphenyl phosphonium bromide (Aldrich 30,585-5), 2-hydroxyethyl triphenyl phosphonium bromide (Aldrich 30,413-1), (2-hydroxyethyl) triphenyl phosphonium chloride (Aldrich H3,065-8), [(R)-(+)-3-hydroxy-2-methyl propyl] triphenyl phosphonium bromide (Aldrich 32,507-4), [(S)-(-)-3-hydroxy-2-methyl propyl] triphenyl phosphonium bromide (Aldrich 32,508-2), (2-hydroxybenzyl triphenyl phosphonium bromide (Aldrich 21,629-1), (formyl methyl) triphenyl phosphonium chloride (Aldrich 30,532-4), (methoxymethyl) triphenyl phosphonium chloride (Aldrich 30,956-7), acetonyl triphenyl phosphonium chloride (Aldrich 15, 807-0), carbomethoxymethyl triphenyl phosphonium bromide (Aldrich 25,906-3), (ethoxy carbonyl methyl) triphenyl phosphonium chloride (Aldrich 30,531-6), carbethoxymethyl triphenyl phosphonium bromide (Aldrich C530-0), (tert-butoxy carbonyl methyl) triphenyl phosphonium bromide (Aldrich 36,904-7), phenacyl triphenyl phosphonium bromide (Aldrich 15,133-5), (4-ethoxybenzyl) triphenyl phosphonium bromide (Aldrich 26,648-5), 4-butoxybenzyl triphenyl phosphonium bromide (Aldrich 27,489-5), 2-(1,3-dioxan-2-yl) ethyl] triphenyl phosphonium bromide (Aldrich 21,959-2), (1,3-dioxolan-2-ylmethyl) triphenyl phosphonium bromide (Aldrich 22,385-9), vinyl triphenyl phosphonium bromide (Aldrich 15,019-3), allyl triphenyl phosphonium bromide (Aldrich A3, 660-3), allyl triphenyl phosphonium chloride (Aldrich 33,351-4), propargyl triphenyl phosphonium bromide (Aldrich 22,648-3), (3-trimethyl silyl-2-propynyl) triphenyl phosphonium bromide (Aldrich 29, 958-8), p-xylylene bis (triphenyl phosphonium bromide) (Aldrich 112-1), and the like. Mixtures of any two or more of the above phosphonium compounds can also be employed. The phosphonium compound is present in any effective amount relative to the substrate. Typically, the phosphonium compound is present in an amount of from about 1 to about 25 percent by weight of the substrate, preferably from about 5 to about 15 percent by weight of the substrate, although the amount can be outside this range. The amount can also be expressed in terms of the weight of phosphonium compound per unit area of substrate. Typically, the phosphonium compound is present in an amount of from about 0.3 to about 7.5 g/m 2 of the substrate surface to which it is applied, and preferably from about 1.5 to about 4.5 g/m 2 of the substrate surface to which it is applied, although the amount can be outside these ranges. Higher concentrations of phosphonium compound are preferred for the purpose of enhancing the color of images printed on the recording sheets; the lower concentrations are adequate for enhancing the waterfastness of images printed on the recording sheets. When the phosphonium compound is applied to the substrate as a coating, the coatings employed for the recording sheets of the present invention can include an optional binder in addition to the phosphonium compound. Examples of suitable binder polymers include (a) hydrophilic polysaccharides and their modifications, such as (1) starch (such as starch SLS-280®, available from St. Lawrence starch), (2) cationic starch (such as Cato-72®, available from National Starch), (3) hydroxyalkylstarch, wherein alkyl has at least one carbon atom and wherein the number of carbon atoms is such that the material is water soluble, preferably from about 1 to about 20 carbon atoms, and more preferably from about 1 to about 10 carbon atoms, such as methyl, ethyl, propyl, butyl, or the like (such as hydroxypropyl starch (#02382, available from Poly Sciences Inc.) and hydroxyethyl starch (#06733, available from Poly Sciences Inc.)), (4) gelatin (such as Calfskin gelatin #00639, available from Poly Sciences Inc.), (5) alkyl celluloses and aryl celluloses, wherein alkyl has at least one carbon atom and wherein the number of carbon atoms is such that the material is water soluble, preferably from 1 to about 20 carbon atoms, more preferably from 1 to about 10 carbon atoms, and even more preferably from 1 to about 7 carbon atoms, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, benzyl, and the like (such as methyl cellulose (Methocel® AM 4, available from Dow Chemical Company)), and wherein aryl has at least 6 carbon atoms and wherein the number of carbon atoms is such that the material is water soluble, preferably from 6 to about 20 carbon atoms, more preferably from 6 to about 10 carbon atoms, and even more preferably about 6 carbon atoms, such as phenyl, (6) hydroxy alkyl celluloses, wherein alkyl has at least one carbon atom and wherein the number of carbon atoms is such that the material is water soluble, preferably from 1 to about 20 carbon atoms, more preferably from 1 to about 10 carbon atoms, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, benzyl, or the like (such as hydroxyethyl cellulose (Natrosol® 250 LR, available from Hercules Chemical Company), and hydroxypropyl cellulose (Klucel® Type E, available from Hercules Chemical Company)), (7) alkyl hydroxy alkyl celluloses, wherein each alkyl has at least one carbon atom and wherein the number of carbon atoms is such that the material is water soluble, preferably from 1 to about 20 carbon atoms, more preferably from 1 to about 10 carbon atoms, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, benzyl, or the like (such as ethyl hydroxyethyl cellulose (Bermocoll®, available from Berol Kem. A.S. Sweden)), (8) hydroxy alkyl alkyl celluloses, wherein each alkyl has at least one carbon atom and wherein the number of carbon atoms is such that the material is water soluble, preferably from 1 to about 20 carbon atoms, more preferably from 1 to about 10 carbon atoms, such as methyl, ethyl, propyl, butyl and the like (such as hydroxyethyl methyl cellulose (HEM®, available from British Celanese Ltd., also available as Tylose® MH, MHK from Kale A.G.), hydroxypropyl methyl cellulose (Methocel® K35LV, available from Dow Chemical Company), and hydroxy butylmethyl cellulose (such as HBMC, available from Dow Chemical Company)), (9) dihydroxyalkyl cellulose, wherein alkyl has at least one carbon atom and wherein the number of carbon atoms is such that the material is water soluble, preferably from 1 to about 20 carbon atoms, more preferably from 1 to about 10 carbon atoms, such as methyl, ethyl, propyl, butyl and the like (such as dihydroxypropyl cellulose, which can be prepared by the reaction of 3-chloro-1,2-propane with alkali cellulose), (10) hydroxy alkyl hydroxy alkyl cellulose, wherein each alkyl has at least one carbon atom and wherein the number of carbon atoms is such that the material is water soluble, preferably from 1 to about 20 carbon atoms, more preferably from 1 to about 10 carbon atoms, such as methyl, ethyl, propyl, butyl and the like (such as hydroxypropyl hydroxyethyl cellulose, available from Aqualon Company), (11) halodeoxycellulose, wherein halo represents a halogen atom (such as chlorodeoxycellulose, which can be prepared by the reaction of cellulose with sulfuryl chloride in pyridine at 25°C), (12) amino deoxycellulose (which can be prepared by the reaction of chlorodeoxy cellulose with 19 percent alcoholic solution of ammonia for 6 hours at 160°C), (13) dialkylammonium halide hydroxy alkyl cellulose, wherein each alkyl has at least one carbon atom and wherein the number of carbon atoms is such that the material is water soluble, preferably from 1 to about 20 carbon atoms, more preferably from 1 to about 10 carbon atoms, such as methyl, ethyl, propyl, butyl and the like, and wherein halide represents a halogen atom (such as diethylammonium chloride hydroxy ethyl cellulose, available as Celquat® H-100, L-200, National Starch and Chemical Company), (14) hydroxyalkyl trialkyl ammonium halide hydroxyalkyl cellulose, wherein each alkyl has at least one carbon atom and wherein the number of carbon atoms is such that the material is water soluble, preferably from 1 to about 20 carbon atoms, more preferably from 1 to about 10 carbon atoms, such as methyl, ethyl, propyl, butyl and the like, and wherein halide represents a halogen atom (such as hydroxypropyl trimethyl ammonium chloride hydroxyethyl cellulose, available from Union Carbide Company as Polymer JR), (15) dialkyl amino alkyl cellulose, wherein each alkyl has at least one carbon atom and wherein the number of carbon atoms is such that the material is water soluble, preferably from 1 to about 20 carbon atoms, more preferably from 1 to about 10 carbon atoms, such as methyl, ethyl, propyl, butyl and the like, (such as diethyl amino ethyl cellulose, available from Poly Sciences Inc. as DEAE cellulose #05178), (16) carboxyalkyl dextrans, wherein alkyl has at least one carbon atom and wherein the number of carbon atoms is such that the material is water soluble, preferably from 1 to about 20 carbon atoms, more preferably from 1 to about 10 carbon atoms, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, and the like, (such as carboxymethyl dextrans, available from Poly Sciences Inc. as #16058), (17) dialkyl aminoalkyl dextran, wherein each alkyl has at least one carbon atom and wherein the number of carbon atoms is such that the material is water soluble, preferably from 1 to about 20 carbon atoms, more preferably from 1 to about 10 carbon atoms, such as methyl, ethyl, propyl, butyl and the like (such as diethyl aminoethyl dextran, available from Poly Sciences Inc. as #5178), (18) amino dextran (available from Molecular Probes Inc), (19) carboxy alkyl cellulose salts, wherein alkyl has at least one carbon atom and wherein the number of carbon atoms is such that the material is water soluble, preferably from 1 to about 20 carbon atoms, more preferably from 1 to about 10 carbon atoms, such as methyl, ethyl, propyl, butyl and the like, and wherein the cation is any conventional cation, such as sodium, lithium, potassium, calcium, magnesium, or the like (such as sodium carboxymethyl cellulose CMC 7HOF, available from Hercules Chemical Company), (20) gum arabic (such as #G9752, available from Sigma Chemical Company), (21) carrageenan (such as #C1013 available from Sigma Chemical Company), (22) Karaya gum (such as #G0503, available from Sigma Chemical Company), (23) xanthan (such as Keltrol-T®, available from Kelco division of Merck and Company), (24) chitosan (such as #C3646, available from Sigma Chemical Company), (25) carboxyalkyl hydroxyalkyl guar, wherein each alkyl has at least one carbon atom and wherein the number of carbon atoms is such that the material is water soluble, preferably from 1 to about 20 carbon atoms, more preferably from 1 to about 10 carbon atoms, such as methyl, ethyl, propyl, butyl and the like (such as carboxymethyl hydroxypropyl guar, available from Auqualon Company), (26) cationic guar (such as Celanese Jaguars® C-14-S, C-15, C-17, available from Celanese Chemical Company), (27) n-carboxyalkyl chitin, wherein alkyl has at least one carbon atom and wherein the number of carbon atoms is such that the material is water soluble, preferably from 1 to about 20 carbon atoms, more preferably from 1 to about 10 carbon atoms, such as methyl, ethyl, propyl, butyl and the like, such as n-carboxymethyl chitin, (28) dialkyl ammonium hydrolyzed collagen protein, wherein alkyl has at least one carbon atom and wherein the number of carbon atoms is such that the material is water soluble, preferably from 1 to about 20 carbon atoms, more preferably from 1 to about 10 carbon atoms, such as methyl, ethyl, propyl, butyl and the like (such as dimethyl ammonium hydrolyzed collagen protein, available from Croda as Croquats®), (29) agar-agar (such as that available from Pfaltz and Bauer Inc), (30) cellulose sulfate salts, wherein the cation is any conventional cation, such as sodium, lithium, potassium, calcium, magnesium, or the like (such as sodium cellulose sulfate #023 available from Scientific Polymer Products), and (31) carboxyalkylhydroxyalkyl cellulose salts, wherein each alkyl has at least one carbon atom and wherein the number of carbon atoms is such that the material is water soluble, preferably from 1 to about 20 carbon atoms, more preferably from 1 to about 10 carbon atoms, such as methyl, ethyl, propyl, butyl and the like, and wherein the cation is any conventional cation, such as sodium, lithium, potassium, calcium, magnesium, or the like (such as sodium carboxymethylhydroxyethyl cellulose CMHEC 43H and 37L available from Hercules Chemical Company); (b) vinyl polymers, such as (1) poly(vinyl alcohol) (such as Elvanol® available from Dupont Chemical Company), (2) poly (vinyl phosphate) (such as #4391 available from Poly Sciences Inc.), (3) poly (vinyl pyrrolidone) (such as that available from GAF Corporation), (4) vinyl pyrrolidone-vinyl acetate copolymers (such as #02587, available from Poly Sciences Inc.), (5) vinyl pyrrolidone-styrene copolymers (such as #371, available from Scientific Polymer Products), (6) poly (vinylamine) (such as #1562, available from Poly Sciences Inc.), (7) poly (vinyl alcohol) alkoxylated, wherein alkyl has at least one carbon atom and wherein the number of carbon atoms is such that the material is water soluble, preferably from 1 to about 20 carbon atoms, more preferably from 1 to about 10 carbon atoms, such as methyl, ethyl, propyl, butyl, and the like (such as poly (vinyl alcohol) ethoxylated #6573, available from Poly Sciences Inc.), and (8) poly (vinyl pyrrolidone-dialkylaminoalkyl alkylacrylate), wherein each alkyl has at least one carbon atom and wherein the number of carbon atoms is such that the material is water soluble, preferably from 1 to about 20 carbon atoms, more preferably from 1 to about 10 carbon atoms, such as methyl, ethyl, propyl, butyl, and the like (such as poly (vinyl pyrrolidone-diethylaminomethylmethacrylate) #16294 and #16295, available from Poly Sciences Inc.); (c) formaldehyde resins, such as (1) melamine-formaldehyde resin (such as BC 309®, available from British Industrial Plastics Limited), (2) urea-formaldehyde resin (such as BC777®, available from British Industrial Plastics Limited), and (3) alkylated urea-formaldehyde resins, wherein alkyl has at least one carbon atom and wherein the number of carbon atoms is such that the material is water soluble, preferably from 1 to about 20 carbon atoms, more preferably from 1 to about 10 carbon atoms, such as methyl, ethyl, propyl, butyl, and the like (such as methylated urea-formaldehyde resins, available from American Cyanamid Company as Beetle® 65); (d) ionic polymers, such as (1) poly (2-acrylamide-2-methyl propane sulfonic acid) (such as #175 available from Scientific Polymer Products), (2) poly (N,N-dimethyl-3,5-dimethylene piperidinium chloride) (such as #401, available from Scientific Polymer Products), and (3) poly (methylene-guanidine) hydrochloride (such as #654, available from Scientific Polymer Products); (e) latex polymers, such as (1) cationic, anionic, and nonionic styrene-butadiene latexes (such as that available from Gen Corp Polymer Products, such as RES 4040® and RES 4100®, available from Unocal Chemicals, and such as DL 6672A®, DL6638A®, and DL6663A®, available from Dow Chemical Company), (2) ethylene-vinylacetate latex (such as Airflex® 400, available from Air Products and Chemicals Inc.), and (3) vinyl acetate-acrylic copolymer latexes (such as synthemul® 97-726, available from Reichhold Chemical Inc, Resyn® 25-1110 and Resyn® 25-1140, available from National Starch Company, and RES® 3103 available from Unocal Chemicals; (f) maleic anhydride and maleic acid containing polymers, such as (1) styrene-maleic anhydride copolymers (such as that available as Scripset® from Monsanto, and the SMA® series available from Arco), (2) vinyl alkyl ether-maleic anhydride copolymers, wherein alkyl has at least one carbon atom and wherein the number of carbon atoms is such that the material is water soluble, preferably from 1 to about 20 carbon atoms, more preferably from 1 to about 10 carbon atoms, such as methyl, ethyl, propyl, butyl, and the like (such as vinyl methyl ether-maleic anhydride copolymer #173, available from Scientific Polymer Products), (3) alkylene-maleic anhydride copolymers, wherein alkylene has at least one carbon atom and wherein the number of carbon atoms is such that the material is water soluble, preferably from 1 to about 20 carbon atoms, more preferably from 1 to about 10 carbon atoms, such as methyl, ethyl, propyl, butyl, and the like (such as ethylene-maleic anhydride copolymer #2308, available from Poly Sciences Inc., also available as EMA® from Monsanto Chemical Company), (4) butadiene-maleic acid copolymers (such as #07787, available from Poly Sciences Inc.), (5) vinylalkylether-maleic acid copolymers, wherein alkyl has at least one carbon atom and wherein the number of carbon atoms is such that the material is water soluble, preferably from 1 to about 20 carbon atoms, more preferably from 1 to about 10 carbon atoms, such as methyl, ethyl, propyl, butyl, and the like (such as vinylmethylether-maleic acid copolymer, available from GAF Corporationas Gantrez® S-95), and (6) alkyl vinyl ether-maleic acid esters, wherein alkyl has at least one carbon atom and wherein the number of carbon atoms is such that the material is water soluble, preferably from 1 to about 20 carbon atoms, more preferably from 1 to about 10 carbon atoms, such as methyl, ethyl, propyl, butyl, and the like (such as methyl vinyl ether-maleic acid ester #773, available from Scientific Polymer Products); (g) acrylamide containing polymers, such as (1) poly (acrylamide) (such as #02806, available from Poly Sciences Inc.), (2) acrylamide-acrylic acid copolymers (such as #04652, #02220, and #18545, available from Poly Sciences Inc.), and (3) poly (N,N-dimethyl acrylamide) (such as #004590, available from Poly Sciences Inc.); and (h) poly (alkylene imine) containing polymers, wherein alkylene has two (ethylene), three (propylene), or four (butylene) carbon atoms, such as (1) poly(ethylene imine) (such as #135, available from Scientific Polymer Products), (2) poly(ethylene imine) epichlorohydrin (such as #634, available from Scientific Polymer Products), and (3) alkoxylated poly (ethylene imine), wherein alkyl has one (methoxylated), two (ethoxylated), three (propoxylated), or four (butoxylated) carbon atoms (such as ethoxylated poly (ethylene imine #636, available from Scientific Polymer Products); and the like, as well as blends or mixtures of any of the above, with starches and latexes being particularly preferred because of their availability and applicability to paper. Any mixtures of the above ingredients in any relative amounts can be employed. If present, the binder can be present within the coating in any effective amount; typically the binder and the phosphonium compound are present in relative amounts of from about 10 percent by weight binder and about 90 percent by weight phosphonium compound to about 50 percent by weight binder and about 50 percent by weight phosphonium compound, although the relative amounts can be outside of this range. In addition, the coating of the recording sheets of the present invention can contain optional filler components. Fillers can be present in any effective amount, and if present, typically are present in amounts of from about 1 to about 60 percent by weight of the coating composition. Examples of filler components include colloidal silicas, such as Syloid® 74, available from Grace Company (preferably present, in one embodiment, in an amount of about 20 weight percent), titanium dioxide (available as Rutile® or Anatase® from NL Chem Canada, Inc.), hydrated alumina (Hydrad® TMC-HBF, Hydrad® TM-HBC, available from J.M. Huber Corporation), barium sulfate (K.C. Blanc Fix® HD80, available from Kali Chemie Corporation), calcium carbonate (Microwhite® Sylacauga Calcium Products), high brightness clays (such as Engelhard Paper Clays), calcium silicate (available from J.M. Huber Corporation), cellulosic materials insoluble in water or any organic solvents (such as those available from Scientific Polymer Products), blend of calcium fluoride and silica, such as Opalex-C® available from Kemira.O.Y, zinc oxide, such as Zoco Fax 183, available from Zo Chem, blends of zinc sulfide with barium sulfate, such as Lithopane®, available from Schteben Company, and the like, as well as mixtures thereof. Brightener fillers can enhance color mixing and assist in improving print-through in recording sheets of the present invention. The coating containing the phosphonium compound is present on the substrate of the recording sheet of the present invention in any effective thickness. Typically, the total thickness of the coating layer is from about 1 to about 25 µm and preferably from about 5 to about 10 µm, although the thickness can be outside of these ranges. The phosphonium compound or the mixture of phosphonium compound, optional binder, and/or optional filler can be applied to the substrate by any suitable technique, such as size press treatment, dip coating, reverse roll coating, extrusion coating, or the like. For example, the coating can be applied with a KRK® size press (Kumagai Riki Kogyo Co., Ltd., Nerima, Tokyo, Japan) by dip coating and can be applied by solvent extrusion on a Faustel® Coater. The KRK® size press is a lab size press that simulates a commercial size press. This size press is normally sheet fed, whereas a commercial size press typically employs a continuous web. On the KRK® size press, the substrate sheet is taped by one end to the carrier mechanism plate. The speed of the test and the roll pressures are set, and the coating solution is poured into the solution tank. A 4 liter stainless steel beaker is situated underneath for retaining the solution overflow. The coating solution is cycled once through the system (without moving the substrate sheet) to wet the surface of the rolls and then returned to the feed tank, where it is cycled a second time. While the rolls are being "wetted", the sheet is fed through the sizing rolls by pressing the carrier mechanism start button. The coated sheet is then removed from the carrier mechanism plate and is placed on a 12 inch by 40 inch (30.5 × 102cm) sheet of 750 µm thick Teflon® for support and is dried on the Dynamic Former® drying drum and held under restraint to prevent shrinkage. The drying temperature is approximately 105°C. This method of coating treats both sides of the substrate simultaneously. In dip coating, a web of the material to be coated is transported below the surface of the liquid coating composition by a single roll in such a manner that the exposed site is saturated, followed by removal of any excess coating by the squeeze rolls and drying at 100°C in an air dryer. The liquid coating composition generally comprises the desired coating composition dissolved in a solvent such as water, methanol, or the like. The method of surface treating the substrate using a coater results in a continuous sheet of substrate with the coating material applied first to one side and then to the second side of this substrate. The substrate can also be coated by a slot extrusion process, wherein a flat die is situated with the die lips in close proximity to the web of substrate to be coated, resulting in a continuous film of the coating solution evenly distributed across one surface of the sheet, followed by drying in an air dryer at 100°C. Recording sheets of the present invention can be employed in ink jet printing processes. One embodiment of the present invention is directed to a process which comprises applying an aqueous recording liquid to a recording sheet of the present invention in an imagewise pattern. Another embodiment of the present invention is directed to a printing process which comprises (1) incorporating into an ink jet printing apparatus containing an aqueous ink a recording sheet of the present invention, and (2) causing droplets of the ink to be ejected in an imagewise pattern onto the recording sheet, thereby generating images on the recording sheet. Ink jet printing processes are well known, and are described in, for example, US-A-s4,601,777, 4,251,824, 4,410,899, 4,412,224, and 4,532,530. In a particularly preferred embodiment, the printing apparatus employs a thermal ink jet process wherein the ink in the nozzles is selectively heated in an imagewise pattern, thereby causing droplets of the ink to be ejected in imagewise pattern. The recording sheets of the present invention can also be used in any other printing or imaging process, such as printing with pen plotters, handwriting with ink pens, offset printing processes, or the like, provided that the ink employed to form the image is compatible with the ink receiving layer of the recording sheet. Specific embodiments of the invention will now be described in detail. These examples are intended to be illustrative, and the invention is not limited to the materials, conditions, or process parameters set forth in these embodiments. All parts and percentages are by weight unless otherwise indicated. The optical density measurements recited herein were obtained on a Pacific Spectrograph Color System®. The system consists of two major components, an optical sensor and a data terminal. The optical sensor employs a 6 inch (15.2cm) integrating sphere to provide diffuse illumination and 8 degrees viewing. This sensor can be used to measure both transmission and reflectance samples. When reflectance samples are measured, a specular component may be included. A high resolution, full dispersion, grating monochromator was used to scan the spectrum from 380 to 720nm. The data terminal features a 12 inch (30.5cm) CRT display, numerical keyboard for selection of operating parameters and the entry of tristimulus values, and an alphanumeric keyboard for entry of product standard information. EXAMPLE I Plain paper sheets (Simpson® alkaline sized, carrying no surface treatments, obtained from Simpson Paper Co., Kalamazoo, MI) measuring 8.5 × 11 inches (21.6 × 28cm) were treated with solutions comprising 2 percent by weight of a phosphonium compound and 98 percent of a solvent (specifically identified for each compound in the table below; meOH = methanol; ratios are by weight) via dip coating and dried in air at 100°C. Subsequent to treatment, each paper sheet had deposited on each side thereof about 100mg of the phosphonium compound. The treated papers, as well as sheets of the Simpson paper which had not been treated with a phosphonium compound, were incorporated into a Hewlett-Packard® PaintJet® ink jet printer and a Xerox® 4020 ink jet printer, and full color prints were generated on each sheet by each printer. The optical density of the cyan, magenta, yellow, and black images were measured. Subsequently, the images were tested for water resistance by washing them at 50°C for 2 minutes with water followed by again measuring the optical densities of the images. The results were as follows: Cmpd. Black Cyan Magenta Yellow Bef. Aft. % WF Bef. Aft. % WF Bef. Aft. % WF Bef. Aft. % WF none 1.11 0.74 67 0.97 0.72 74 1.01 0.48 48 0.75 0.62 83 1 1.14 1.06 93 0.91 0.90 99 1.03 0.88 85 0.72 0.71 99 2 1.02 0.97 95 0.85 0.83 98 0.99 0.88 89 0.66 0.62 94 3 1.13 1.00 88 1.01 0.97 96 1.05 0.86 82 0.75 0.71 95 4 1.17 1.00 85 0.94 0.90 96 1.06 0.74 70 0.70 0.68 97 5 1.13 1.00 88 0.90 0.93 103 1.06 0.92 87 0.68 0.69 101 6 1.13 1.04 92 0.92 0.98 107 1.09 0.91 83 0.74 0.72 97 7 0.92 0.93 101 0.78 0.78 100 0.85 0.82 96 0.60 0.57 95 8 1.14 1.08 95 0.92 0.87 95 1.04 0.99 95 0.68 0.66 97 9 1.17 1.12 96 1.03 0.91 88 1.06 1.05 99 0.80 0.72 90 optical density and waterfastness of coated papers printed with Xerox® 4020 ink jet printer Cmpd. Black Cyan Magenta Yellow Bef. Aft. % WF Bef. Aft. % WF Bef. Aft. % WF Bef. Aft. % WF none 1.04 0.60 58 1.15 0.54 47 0.87 0.72 83 0.55 0.54 98 1 1.13 0.85 75 1.22 0.63 56 1.00 1.00 100 0.62 0.62 100 2 1.12 1.03 92 1.22 0.96 79 1.00 0.95 95 0.63 0.61 97 3 1.13 0.65 58 1.25 0.79 63 0.98 0.95 97 0.63 0.60 95 4 1.14 0.77 68 1.24 0.62 50 0.99 1.01 102 0.63 0.62 98 5 1.12 0.70 63 1.25 0.64 51 0.99 0.97 98 0.63 0.63 100 6 1.11 0.82 74 1.25 0.71 57 0.99 0.98 99 0.62 0.61 98 7 1.00 0.91 91 1.17 0.79 68 0.90 0.86 96 0.64 0.59 92 8 1.12 0.81 72 1.20 0.58 48 0.98 0.99 101 0.62 0.60 97 9 1.14 1.08 95 1.27 1.23 97 1.02 0.96 94 0.66 0.61 92 optical density and waterfastness of coated papers printed with H-P PaintJet® ink jet printer # Compound Solvent 1 propyl triphenyl phosphonium bromide (Aldrich 13, 156-3) H 2 O 2 benzyl triphenyl phosphonium chloride (Aldrich B3,280-7) H 2 O 3 (2-hydroxybenzyl) triphenyl phosphonium bromide (1% solution) (Aldrich 21,629-1) 50:50 H 2 O/meOH 4 (2-(1,3-dioxan-2-yl)ethyl) triphenyl phosphonium bromide (Aldrich 21,959-2) H 2 O 5 vinyl triphenyl phosphonium bromide (Aldrich 15,019-3) H 2 O 6 propargyl triphenyl phosphonium bromide (Aldrich 22,648-3) H 2 O 7 p-xylylene bis(triphenyl phosphonium bromide) (Aldrich 112-1) meOH 8 tetraphenyl phosphonium chloride (Aldrich 21,879-0) H 2 O 9 stearyl tributyl phosphonium bromide (Aldrich 29,303-2) 30:70 H 2 O/meOH As the data indicate, the sheets treated with the phosphonium compounds generally exhibited superior waterfastness compared to those sheets not treated with a phosphonium compound.

Claims: A printing process which comprises applying a recording liquid to a recording sheet comprising a base sheet and a phosphonium compound, in an imagewise pattern, characterised by comprising (1) incorporating the recording sheet into an ink jet printing apparatus containing an aqueous ink, and (2) causing droplets of the ink to be ejected in an imagewise pattern onto the recording sheet, thereby generating images on the recording sheet. A process according to claim 1, further including a pigment and/or a binder. A process according to claim 1 or 2 wherein the base sheet is (1) paper, or (2) transparent. A process according to claim 1, 2 or 3 wherein the phosphonium compound is selected from the group consisting of wherein R is an alkyl group, X is an anion, and all four R groups are the same; wherein R is an alkyl group, wherein all three R groups are the same, wherein R is not the same as R', X is an anion, and R' is selected from the group consisting of alkyl groups, substituted alkyl groups, arylalkyl groups, and substituted arylalkyl groups; wherein Ar is an aryl group or a substituted aryl group, X is an anion, and all four Ar groups are the same; wherein Ar is an aryl group or a substituted aryl group, wherein all three Ar groups are the same, X is an anion, and R' is selected from the group consisting of alkyl groups, substituted alkyl groups, arylalkyl groups, and substituted arylalkyl groups; and mixtures thereof. A process according to claim 4 wherein R' is selected from the group consisting of alkyl groups with from 1 to about 25 carbon atoms, arylalkyl groups with from 7 to about 25 carbon atoms, substituted alkyl groups with from 1 to about 25 carbon atoms, substituted arylalkyl groups with from 7 to about 25 carbon atoms. A process according to claim 4 or 5 wherein the substituents on R' and Ar are selected from the group consisting of silyl groups, halide atoms, nitro groups, amine groups, hydroxy groups, ether groups, aldehyde groups, ketone groups, ester groups, amide groups, carboxylic acid groups, and mixtures thereof. A process according to claim 2 or 3 wherein the phosphonium compound is selected from the group consisting of tetramethyl phosphonium bromide, tetramethyl phosphonium chloride, tetraethyl phosphonium bromide, tetraethyl phosphonium chloride, tetraethyl phosphonium iodide, tetrabutyl phosphonium bromide, tetrabutyl phosphonium chloride, hexadecyl tributyl phosphonium bromide, stearyl tributyl phosphonium bromide, tetraphenyl phosphonium bromide, tetraphenyl phosphonium chloride, tetraphenyl phosphonium Iodide, methyl triphenyl phosphonium bromide, methyl triphenyl phosphonium iodide, ethyl triphenyl phosphonium bromide, n-propyl triphenyl phosphonium bromide, isopropyl triphenyl phosphonium iodide, cyclopropyl triphenyl phosphonium bromide, n-butyl triphenyl phosphonium bromide, isobutyl triphenyl phosphonium bromide, hexyl triphenyl phosphonium bromide, benzyl triphenyl phosphonium chloride, bromomethyl triphenyl phosphonium bromide, chloromethyl triphenyl phosphonium chloride, 3-bromopropyl triphenyl phosphonium bromide, 3-bromobutyl triphenyl phosphonium bromide, 4-bromobutyl triphenyl phosphonium bromide, 2-dimethyl aminoethyl triphenyl phosphonium bromide, [(3-dimethyl amino) propyl] triphenyl phosphonium bromide, 2-hydroxyethyl triphenyl phosphonium bromide, (2-hydroxyethyl) triphenyl phosphonium chloride, [(R)-(+)-3-hydroxy-2-methyl propyl] triphenyl phosphonium bromide, [(S)-(-)-3-hydroxy-2-methyl propyl] triphenyl phosphonium bromide, (2-hydroxybenzyl triphenyl phosphonium bromide, (formyl methyl) triphenyl phosphonium chloride, (methoxymethyl) triphenyl phosphonium chloride, acetonyl triphenyl phosphonium chloride, carbomethoxymethyl triphenyl phosphonium bromide, (ethoxy carbonyl methyl) triphenyl phosphonium chloride, carbethoxymethyl triphenyl phosphonium bromide, (tert-butoxy carbonyl methyl) triphenyl phosphonium bromide, phenacyl triphenyl phosphonium bromide, (4-ethoxybenzyl) triphenyl phosphonium bromide, 4-butoxybenzyl triphenyl phosphonium bromide, 2-(1,3-dioxan-2-yl) ethyl] triphenyl phosphonium bromide, (1,3-dioxolan-2-ylmethyl) triphenyl phosphonium bromide, vinyl triphenyl phosphonium bromide, allyl triphenyl phosphonium bromide, allyl triphenyl phosphonium chloride, propargyl triphenyl phosphonium bromide, (3-trimethyl silyl-2-propynyl) triphenyl phosphonium bromide, p-xylylene bis (triphenyl phosphonium bromide), and mixtures thereof. A process according to any of the preceding claims wherein the phosphonium compound is present in an amount of (1) from about 1 to about 25 percent by weight of the substrate, or (2) from about 5 to about 15 percent by weight of the substrate. A process according to any of the preceding claims wherein the phosphonium compound is present in an amount of from about 0.3 to about 7.5 grams per square meter of the substrate surface to which it is applied.

Inventors: BRYANT BRENT S, MALHOTRA SHADI L, WEISS DORIS K, BRYANT, BRENT S., MALHOTRA, SHADI L., WEISS, DORIS K.
Applicants: XEROX CORP, XEROX CORPORATION
Application year: 1994
Main classification: B41M1
IPC codes: B41M5